DE2241395A1 - 0-PYRAZOLOPYRIMIDINE (THIONO) PHOSPHORUS (PHOSPHONE) ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDES - Google Patents
0-PYRAZOLOPYRIMIDINE (THIONO) PHOSPHORUS (PHOSPHONE) ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDESInfo
- Publication number
- DE2241395A1 DE2241395A1 DE2241395A DE2241395A DE2241395A1 DE 2241395 A1 DE2241395 A1 DE 2241395A1 DE 2241395 A DE2241395 A DE 2241395A DE 2241395 A DE2241395 A DE 2241395A DE 2241395 A1 DE2241395 A1 DE 2241395A1
- Authority
- DE
- Germany
- Prior art keywords
- thiono
- phosphorus
- active ingredient
- pyrazolopyrimidine
- acid ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 150000002148 esters Chemical class 0.000 title claims description 14
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 10
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- ZSQZLMGTNQMFAH-UHFFFAOYSA-N 2-hydroxypyrazolo[4,3-d]pyrimidine Chemical class N1=CN=CC2=NN(O)C=C21 ZSQZLMGTNQMFAH-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YJCXKNNURGCXFQ-UHFFFAOYSA-N ethoxy(ethyl)phosphinic acid Chemical compound CCOP(O)(=O)CC YJCXKNNURGCXFQ-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- YYJNOYZRYGDPNH-MFKUBSTISA-N fenpyroximate Chemical compound C=1C=C(C(=O)OC(C)(C)C)C=CC=1CO/N=C/C=1C(C)=NN(C)C=1OC1=CC=CC=C1 YYJNOYZRYGDPNH-MFKUBSTISA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000020044 madeira Nutrition 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N methyl iso-propyl ketone Natural products CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- HIAMVJKQWYQPAJ-UHFFFAOYSA-N phenyl(propoxy)phosphinic acid Chemical compound CCCOP(O)(=O)C1=CC=CC=C1 HIAMVJKQWYQPAJ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
- A01N57/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Leverkusen, BayerwerkLeverkusen, Bayerwerk
ZentralbereichCentral area
Patente, Marken und LizenzenPatents, trademarks and licenses
Hu/HMHu / HM
ia 2 2. Aug. 1972ia 2 Aug. 2, 1972
0-Pyrazolopyrimidin-(thiono)-phosphor(phosphon)-säureester, Verfahren zu ihrer Herstellung sowie ihre Verwendung als Insektizide und Akarizide0-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid ester, Process for their production and their use as insecticides and acaricides
Die vorliegende Erfindung betrifft neue O-Pyrazolopyrimidin-(thiono)-phosphor(phosphon)säureester, welche insektizide und akarizide Eigenschaften "besitzen sowie ein Verfahren zu ihrer Herstellung,The present invention relates to new O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters, which insecticidal and acaricidal properties "have and a method for their manufacture,
Es ist bereits bekannt, daß O-Pyrazolopyrimidin-(thiono)-phosphor(phosphon, phosphin)säureesterderivate, z.B. 0,0-Diäthyl-0-/5,7-dimethylpyrazolo(1,5-oQ-pyrimidin-(2)yl_7-thiono-phosphor- und O-Athylathan-O-Zij^-dimethylpyrazolo-(1,5ö()-pyrimidin-(2)yl_7-thionophosphonsäureester eine pestizide, insbesondere insektizide und akarizide Wirkung aufweisen, (vgl. Belgische Patentschrift 676.802 und offengelegte niederländische Patentanmeldung 6.516.907).It is already known that O-pyrazolopyrimidine- (thiono) -phosphorus (phosphon, phosphinic) acid ester derivatives, e.g. 0,0-diethyl-0- / 5,7-dimethylpyrazolo (1,5-oQ-pyrimidin- (2) yl_7-thiono-phosphorus- and O-Ethylathane-O-Zij ^ -dimethylpyrazolo- (1,5o () - pyrimidin- (2) yl-7-thionophosphonic acid ester have a pesticidal, in particular insecticidal and acaricidal effect, (see Belgian patent specification 676.802 and published Dutch Patent application 6,516,907).
Es wurde nun gefunden, daß die neuen O-Pyrazolopyrimidin-(thiono)-phosphor(phosphon)säureester der FormelIt has now been found that the new O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters the formula
Ie A U 595 - 1 - Ie AU 595 - 1 -
4-0 9809/12364-0 9809/1236
in welcher R1 Alkyl mit 1 bis 6, R, Alkyl mit 1 bis 4 oder Alkoxy mit 1 bis 6 Kohlenstoffatomen bzw. Phenyl, R, ein Wasserstoff-, Chlor- oder Brom- und X ein Sauerstoff- oder Schwefelatom bedeutet,in which R 1 is alkyl with 1 to 6, R, alkyl with 1 to 4 or alkoxy with 1 to 6 carbon atoms or phenyl, R is a hydrogen, chlorine or bromine and X is an oxygen or sulfur atom,
starke insektizide und akarizide Eigenschaften besitzen.have strong insecticidal and acaricidal properties.
Weiterhin wurde gefunden, daß die O-Pyrazolopyrimidin-(thiono)-phosphor(phosphon)säureesterderivate der Konstitution (i) erhalten werden, wenn man (Thiono)Phosphor(phosphon)· säureesterhalogenide der FormelIt has also been found that the O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid ester derivatives of constitution (i) can be obtained if (thiono) phosphorus (phosphon) acid ester halides of the formula
R1O XR 1 OX
NP-Hal (II) N P-Hal (II)
R2 R 2
mit 2-Hydroxypyrazolopyrimidinderivaten der Formelwith 2-hydroxypyrazolopyrimidine derivatives of the formula
JLJJLJ
01,01,
Le A U 595 - 2 - Le AU 595 - 2 -
409809/1236409809/1236
in welchen Formeln R1, Rp9 R, und X die oben angegebene Bedeutung haften und Hai für ein Halogen-, vorzugsweise Ohioratom steht,in which formulas R 1 , Rp 9 R, and X have the meaning given above and Hal stands for a halogen, preferably an atom,
in Anwesenheit eines Säureakzeptors oder in JOrm der entsprechenden Alkali-, Erdalkali- oder Ammoniumsalze umsetzt.in the presence of an acid acceptor or in the JOrm of the corresponding Reacts alkali, alkaline earth or ammonium salts.
Überraschenderweise zeigen die erfindungsgemäßen O-Pyrazolopyrimidin-(thiono)-phosphor(phosphon)säureester der Konstitution (i) eine erheblich höhere insektizide, speziell bodeninsektizide und akarizlde Wirkung als vorbekannte Verbindungen analoger Konstitution und gleicher Wirkungsrichtung. Die erfindungsgemäßen Stoffe stellen somit eine echte Bereicherung der Technik dar.Surprisingly, the O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters according to the invention show the constitution (i) a considerably higher insecticidal, especially soil insecticidal and acaricidal action than previously known compounds analogous constitution and the same direction of action. The substances according to the invention are therefore a real asset of technology.
Außerdem tragen die erfindungsgemäßen Verbindungen zur Erniedrigung des großen Bedarfs >an immer neuen Wirkstoffen auf dem Gebiet der Schädlingsbekämpfungsmittel bei. Letzterer kommt dadurch zustande, daß an die im Handel befindlichen Mittel gerade auch im Hinblick auf Prägen des Umweltschutzes immer höhere Anforderungen gestellt werden, wie geringe^ Warmblüter- und Phytotoxizität, schneller Abbau in und auf'der Pflanze in kurzen Karenzzeiten, Wirksamkeit gegen resistente Schädlinge usw..In addition, the compounds according to the invention contribute to the reduction the great need> for more and more new active ingredients in the field of pesticides. The latter is due to the fact that to those in the trade Means, especially with a view to shaping environmental protection, ever higher demands are made, such as low ^ Warm-blooded animals and phytotoxicity, rapid degradation in and on the Plant in short waiting periods, effectiveness against resistant pests, etc.
Verwendet man O-Äthyläthanphosphonsäureesterchlorid und 2-Hydroxy-5-methyl-pyrazolo(i,5-rt)-pyrimidin als Ausgangsstoffe, so kann der Reaktionsverlauf durch das folgende Pormelschema wiedergegeben werden:If O-ethylethane phosphonic acid ester chloride and 2-hydroxy-5-methyl-pyrazolo (i, 5-rt) -pyrimidine are used as starting materials, the course of the reaction can be indicated by the following formula scheme be reproduced:
Le A U 595 - 3 - Le AU 595 - 3 -
4098040980
HOHO
CH,CH,
Die zu verwendenden Ausgangsstoffe sind durch die Formeln (II) und (III) eindeutig allgemein definiert.The starting materials to be used are indicated by the formulas (II) and (III) are clearly defined in general terms.
Vorzugsweise steht R1 darin jedoch für gerade oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen, während Rp bevorzugt Alkyl mit 1 bis 3 oder Alkoxy mit 1 bis 4 Kohlenstoffatomen bzw. Phenyl und R, Wasserstoff, Chlor oder Brote bedeuten.Preferably, however, R 1 therein stands for straight or branched alkyl radicals with 1 to 4 carbon atoms, while Rp preferably stands for alkyl with 1 to 3 or alkoxy with 1 to 4 carbon atoms or phenyl and R, hydrogen, chlorine or bread.
Als Beispiele für verwendbare (ThionoJPhosphorCphosphonJsäureesterhalogenide (II) seien im einzelnen genannt:As examples of usable (thionophosphorus phosphonic acid ester halides (II) are mentioned in detail:
0,0-Dimethyl-, 0,0-Diäthyl-, 0,0-Dipropyl-, 0,0-Di-iso-propyl-, 0,0-Dibutyl-, O,O-Di-tert.-butyl-, 0-Methyl-O-äthyl-, O-Methyl-0-iso-propyl-, O-Methyl-0-butyl-, 0-Äthyl-O-iso-propyl-, O-Äthyl-O-butylphosphorsäureesterchlorid bzw. -bromid und deren Thionoanaloge, ferner0,0-dimethyl-, 0,0-diethyl-, 0,0-dipropyl-, 0,0-di-iso-propyl-, 0,0-dibutyl-, O, O-di-tert-butyl-, 0-methyl-O-ethyl-, O-methyl-0-iso-propyl-, O-methyl-0-butyl-, 0-ethyl-O-iso-propyl-, O-ethyl-O-butylphosphoric acid ester chloride or bromide and their thiono analogs, furthermore
0-Methyl-methan-, O-Methyl-äthan-, O-Äthyl-methan-, 0-Propylmethan-, O-Propyl-äthan-, O-iso-Propyl-methan-, 0-iso-Propyl-äthan-, O-Butyl-methan-, O-Butyl-äthan-, O-tert.-Butylmethan-, O-Äthyl-iso-propan-, O-MethyI-phenyl-, O-Äthyl-phenyl-, O-Propyl-phenylphosphonsäureesterchlorid bzw. -bromid und die entsprechenden Thionoanalogen.0-methyl-methane, O-methyl-ethane, O-ethyl-methane, 0-propyl methane, O-propyl-ethane, O-iso-propyl-methane, 0-iso-propyl-ethane, O-butyl methane, O-butyl ethane, O-tert-butyl methane, O-ethyl-iso-propane, O-methyl-phenyl-, O-ethyl-phenyl-, O-propyl-phenylphosphonic acid ester chloride or bromide and the corresponding thiono analogs.
Le A 14 595 - 4 - Le A 14 595 - 4 -
409809/123Ö409809 / 123Ö
Die als Ausgangsstoffe zu verwendenden (Thiono)Phosphor-(phosphon)säureesterhalogenide (II) sind-bekannt und können nach üblichen Verfahren hergestellt werden. Die 2-Hydroxypyrazolo-pyrimidine (III) werden aus 3-Hydroxy-5-amino-pyrazol und Formylacetonnatrium sowie gegebenenfalls anschließende Halogenierung in 5-Stellung gewonnen.The (thiono) phosphorus (phosphonic) acid ester halides to be used as starting materials (II) are known and can be prepared by customary processes. The 2-hydroxypyrazolo-pyrimidines (III) are made from 3-hydroxy-5-aminopyrazole and formylacetone sodium and, if appropriate, subsequent halogenation won in 5 position.
Das Herstellungsverfahren für die neuen Stoffe (i) wird bevorzugt unter Mitverwendung geeigneter Lösungs- bzw. Verdünnungsmittel durchgeführt. Als solche kommen praktisch alle inerten organischen Sölventien in Frage. Hierzu gehören vor allem aliphatische und aromatische, gegebenenfalls chlorierte Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Benzin, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol, ■ Äther, z.B. Diäthyl- und Dibutylather, Dioxan, ferner Ketone, beispielsweise Aceton, Methyläthyl-, Methylisopropyl- und Methylisobutylketon, insbesondere Nitrile, wie Aceto- und Propionitril.The manufacturing process for the new substances (i) is preferred carried out with the use of suitable solvents or diluents. Practically everyone comes as such inert organic solvents in question. These include above all aliphatic and aromatic, optionally chlorinated Hydrocarbons such as benzene, toluene, xylene, gasoline, methylene chloride, Chloroform, carbon tetrachloride, chlorobenzene, ■ ethers, e.g. diethyl and dibutyl ethers, dioxane, also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, especially nitriles, such as aceto and Propionitrile.
Als Säureakzeptoren können alle üblichen Säurebindemittel Verwendung finden. Besonders bewährt haben sieh Alkalicarbonate und -alkoholate, wie Natrium- und Kaliumcarbonat, -methylat bzw. -äthylat, ferner aliphatische, aromatische oder heterocyclische Amine, beispielsweise Triethylamin, Dirnethylamin, Dimethylanilin, Dimethylbenzylamin und Pyridin.All customary acid binders can be used as acid acceptors. Alkali carbonates have proven particularly effective and alcoholates, such as sodium and potassium carbonate, methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.
Die Reaktionstemperatur kann innerhalb eines größeren Bereiches variiert werden. Im allgemeinen arbeitet man zwischen 0 und 100, vorzugsweise bei 25 bis 65 C.The reaction temperature can be within a wide range can be varied. In general, one works between 0 and 100, preferably at 25 to 65 C.
Die Umsetzung wird im allgemeinen bei Normaldruck vorgenommen.The reaction is generally carried out under normal pressure.
Le A U 595 - 5 - Le AU 595 - 5 -
A09809/12A09809 / 12
Zur Durchführung des Verfahrens setzt man.die Ausgangsstoffe meist in äquimolaren Verhältnissen ein. Ein Überschuß der einen oder anderen Reaktionskomponente bringt keine wesentlichen Vorteile. Die Umsetzung wird bevorzugt in Gegenwart eines der oben genannten Lösungsmittel sowie in Anwesenheit eines Säureakzeptors bei den angegebenen Temperaturen vorgenommen und das Reaktionsgemisch nach mehrstündigem RUhren in üblicher Weise aufgearbeitet.The starting materials are used to carry out the process mostly in equimolar proportions. An excess of one or the other reaction component does not bring about any significant Advantages. The reaction is preferably carried out in the presence and in the presence of one of the abovementioned solvents made of an acid acceptor at the stated temperatures and the reaction mixture after stirring for several hours worked up in the usual way.
Die erfindungsgemäßen Stoffe fallen in kristalliner Form an. Zu ihrer Charakterisierung dient der Schmelzpunkt.The substances according to the invention are obtained in crystalline form. The melting point is used to characterize them.
Wie bereits mehrfach erwähnt, zeichnen sich die neuen O-Pyrazolopyrimidin-(thiono)-phosphor(phosphon)säureeöter durch eine hervorragende insektizide, speziell bodeninsektizide und akarizide Wirksamkeit gegenüber Pflanzen-, Hygiene- und Vorrats Schädlingen aus. Sie besitzen dabei so.wohl eine gute Wirkung gegen saugende als auch beißende Insekten und Milben (Acarina). Gleichzeitig weisen sie eine geringe Phytotoxizität auf.As already mentioned several times, the new O-pyrazolopyrimidine- (thiono) -phosphorus (phosphonic) acid removers stand out due to an excellent insecticidal, especially soil insecticidal and acaricidal effectiveness against plants, hygiene and supplies Pests out. They have a good effect against sucking as well as biting insects and mites (Acarina). At the same time, they have low phytotoxicity.
Aus diesen Gründen werden die erfindungsgemäßen Produkte mit Erfolg als Schädlingsbekämpfungsmittel im Pflanzen- und Vorratsschutz sowie auf dem Hygienesektor eingesetzt.For these reasons, the products according to the invention Used successfully as a pesticide in the protection of plants and stored products as well as in the hygiene sector.
Le A 14 595 - 6 - Le A 14 595 - 6 -
409809/1236409809/1236
Zu den saugenden Insekten gehören im wesentlichen Blattläuse
(Aphidae) wie die grüne Pfirsichblattlaus (Myzus persicae)^ ·
die schwarze Bohnen- (Doralis fabae)^ Hafer- (Rhopaloslphum
padi), Erbsen- (Macrosiphum plsi) und Kartofifellaus (Macrosiphum
solanifolii), ferner di@ Johannisbeergallen- (Cryptomyzus korschelti), mehlige Apfel- (Sappaphis mali)„ mehlige Pflaumen-(Hyalopterus
arundinis) und schwarze Kirschenblattlaus (Myzus cerasi), außerdem Schild- und Schmierläuse (Coccina), z.B. die
Efeuschild- (Aspidiotus hederae) und Napfschildlaus (Lecanium
hesperidum) sowie die Schmierlaus (Pseudccocenas maritimus);
Blasenfüße (Thysanoptera) wie Hercinothrips femoralis und
Wanzen, beispielweeise die Rüben- (Piesma quadrata)^ Baumwoll-(Dysdercus
intermedius), Bett- (Cimex lectularius), Raub-(Rhodnius
prolixus) und Chagaswanze (Triatoma infestans),
ferner Zikaden, wie Euscelis bilobatus und Nephotettix bipunctatus.
The sucking insects mainly include aphids
(Aphidae) such as the green peach aphid (Myzus persicae) ^ ·
the black bean (Doralis fabae) ^ oat (Rhopaloslphum
padi), pea (Macrosiphum plsi) and potato lice (Macrosiphum solanifolii), also di @currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), also Scale lice and mealybugs (Coccina), for example the ivy shield louse (Aspidiotus hederae) and cup lice (Lecanium hesperidum) and the mealybug (Pseudccocenas maritimus);
Bladder feet (Thysanoptera) such as Hercinothrips femoralis and
Bed bugs, for example the beet bugs (Piesma quadrata) ^ cotton bugs (Dysdercus intermedius), bed bugs (Cimex lectularius), predatory bugs (Rhodnius prolixus) and chagas bugs (Triatoma infestans),
also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.
Bei den beißenden Insekten wären vor allem zu nennen Schmetterlingsraupen
(L©pidoptera) wi© di@ Kohlschabe (Plutella maculipennis),
der Schwammspinner (Lymantria dispar), Goldafter
(Euproctis chrysorrhoea) und Ringelspinner (Malacosoma neustria),
weiterhin die Kohl- (-Mamestra brassicae) und die Saateule (Agrotis segetum), der große Kohlweißling (Pleris brassicae),
kleine Frostspanner (Cheimatobia brumata), Eichenwickler (Tortrix viridana), der Heer- (Laphygma frugiperda) und aepyptische
Baumwollwurm (Prodenia litura), ferner die Gespinst-(Hyponomeuta
padella), Mehl- (Ephestia kühniella ) und große
Wachsmotte (Galleria mellonella),Among the biting insects, butterfly caterpillars (L © pidoptera) wi © di @ cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), gold juicers should be mentioned in particular
(Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (-Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pleris brassicae), small frost moth (Cheimatobia brumata), oak moth (Tortrix viridana), the Army (Laphygma frugiperda) and aepyptic cotton worms (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large ones
Wax moth (Galleria mellonella),
Le A 14 595 - 7 " Le A 14 595 - 7 "
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Weiterhin zählen zu den beißenden Insekten Käfer (Coleoptera) z.B. Korn- (Sitophilus granarius = Calandra granaria), Kartoffel- (Leptinotarsa decemlineata), Ampfer- (Gastrophysa viridula), Meerrettichblatt- (Phaedon cochleariae), Rapsglanz-(Meligethes aeneus), Himbeer- (Byturus tomentosus), Speisebohnen- (Bruchidius = Acanthoscelides obtectus), Speck-(Derraestea frischi), Khapra- (Trogoderma granarium), rotbrauner Reismehl- (Tribolium castaneum), Mais- (Calandra oder Sitophilus zeamais), Brot- (Stegobium paniceum), gemeiner Mehl- (Tenebrio molitor) und Getreideplattkäfer (Oryzaephilus surinamensis), aber auch im Boden lebende Arten z. B. Drahtwürmer (Agriotes spec.) und Engerlinge (Melolontha melolontha); Schaben wie die Deutsche (Blattella germanica), Amerikanische (Periplaneta amerlcana), Madeira- (Leucophaea oder Rhyparobia maderae), Orientalische (Blatta orientalis), Riesen- (Blaberus giganteus) und schwarze Riesenschabe (Blaberus fuscus) sowie Henschoutedenia flexivitta; ferner Orthopteren z.B. das Heimchen (Gryllus domesticus); Termiten wie die Erdtermite (Reticulitermes flavipes) und Hymenopteren wie Ameisen, beispielsweise die Wiesenameise (Lasius niger).Furthermore, the biting insects include beetles (Coleoptera) e.g. grain (Sitophilus granarius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table beans (Bruchidius = Acanthoscelides obtectus), bacon (Derraestea frischi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread beetle (Stegobium paniceum), common flour beetle (Tenebrio molitor) and flat grain beetle (Oryzaephilus surinamensis), but also species living in the ground such. B. wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like that German (Blattella germanica), American (Periplaneta amerlcana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatta orientalis), giant cockroach (Blaberus giganteus) and black cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; also Orthoptera e.g. the cricket (Gryllus domesticus); Termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera such as ants, for example the meadow ant (Lasius niger).
Die Dipteren umfassen im wesentlichen Fliegen wie die Tau-(Drosophila melanogaster), Mittelmeerfrucht- (Ceratitis capitata), Stuben- (Musca domestica), kleine Stuben- (Fannia canicularis), Glanz- (Phormia regina) und Schmeißfliege (Calliphora erythrocephala) sowie den Wadenstecher (Stomoxys calcltrans); ferner Mücken, z.B. Stechmücken wie die Gelbfieber- (Aedes aegypti), Haus- (Culex pipiens) und Malariamücke (Anopheles Stephens!)„The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small room (Fannia canicularis), glossy fly (Phormia regina) and blowfly (Calliphora erythrocephala) and the calf stick (Stomoxys calcltrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anopheles Stephens!) "
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Zu den Milben (Acari) zählen besonders die Spinnmilben (Tetranychidae) wie die Bohnen- (Tetranychus telarius = Tetranychus althaeae oder Tetranychus urticae) und die Obstbaumspinnmilbe (Paratetranychus pilosus.= Panonychus ulmi), Gallmilben, z.3. die Johannisbeergallmilbe (Eriophyes ribis) und Tarsonemiden beispielsweise die Triebspitzenmilbe (Hemitarsonemus latus) und Cyclamenmilbe (Tarsonemus pallidus); schließlich Zecken wie die Lederzeqke (Ornithodorus moubata).The mites (Acari) include especially the spider mites (Tetranychidae) such as the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus. = Panonychus ulmi), Gall mites, e.g. 3. the currant mite (Eriophyes ribis) and tarsonemids, for example, the shoot tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); finally ticks like the Lederzeqke (Ornithodorus moubata).
Bei der Anwendung gegen Hygiene- und Vorratsschädlinge, besonders Fliegen und Mücken, zeichnen sich die Verfahrensprodukte außerdem durch eine hervorragende Residualwirkung auf Holz und Ton sowie eine gute Alkalistabilität auf gekalkten Unterlagen aus.When used against hygiene and storage pests, especially flies and mosquitoes, the process products are also characterized by an excellent residual effect on wood and clay as well as good alkali stability on limed substrates.
Le A 14595 - 9Le A 14595 - 9
Die erfindungsgemäßen Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate. Diese werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z. B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen infrage: Aromaten, wie Xylol, Toluol, Benzol oder Alkyl= naphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclo= hexan, oder Paraffine, z. B. Erdölfraktionen, Alkohole, wie Butanol oder Glykol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclo= hexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dirnethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z. B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe, z. B. Freon; als feste Trägerstoffe: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde, und synthetische Gesteinamehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als Emulgier- und/oder schaumerzeugende Mittel: nichtionogene und anionische Emulgatoren, wie Folyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol-Äther, z. B. Alkylaryl-polyglykoläther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z. B. Lignin, Sulfitablaugen und Methylcellulose.The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These will produced in a known manner, e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of Use of water as an extender can be, for. B. also used organic solvents as auxiliary solvents will. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkyl = naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or Methylene chloride, aliphatic hydrocarbons such as cyclo = hexane, or paraffins, e.g. B. petroleum fractions, alcohols, such as Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo = hexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous Extenders or carriers are liquids which are meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants such as halogenated hydrocarbons, e.g. B. Freon; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or Diatomaceous earth, and synthetic stone powders, such as finely divided silica, aluminum oxide and silicates; as emulsifying and / or foam-generating agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. B. lignin, sulphite waste liquors and methyl cellulose.
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Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 <fo. The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90% by weight .
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder in den daraus bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, emulgierbare Konzentrate, Emulsionen, Schäume, Suspensionen, Spritzpulver, Pasten, lösliche Pulver, Stäubemittel und Granulate, angewendet werden. Die Anwendung geschieht in üblicher Weise, z. B. durch Verspritzen, Versprühen, Vernebeln, Verstäuben,' Verstreuen, Verräuchern, Vergasen, Gießen, Beizen oder Inkrustieren.The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use Solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, Dusts and granules. It is used in the usual way, for. B. by spraying, spraying, Fogging, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden. Im allgemeinen liegen sie zwischen 0,0001 und 10 $, vorzugsweise zwischen 0,01 und 1 $.The active ingredient concentrations in the ready-to-use preparations can be varied in larger areas. Generally they are between $ 0.0001 and $ 10, preferably between $ 0.01 and $ 1.
Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wo es möglich ist, Formulierungen bis zu 95 i» oder sogar den 100 $igen Wirkstoff allein auszubringen.The active compounds can also be used successfully ultra-low-volume process (ULV) in which it is possible up to 95 i "or even the $ 100 pure active compound apply formulations alone.
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224139S224139S
Beispiel A
Drosophila Test Example A.
Drosophila test
lösungsmittel: 3 Gewichtsteile Aceton Emulgator: 1 Gewichtsteil Alkylarylpolyglykoläthersolvent: 3 parts by weight acetone emulsifier: 1 part by weight alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichteteil Wirkstoff mit der angegebenen Menge Lösungsmittel, das die angegebene Menge Emulgator enthält, und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.For the production of an appropriate preparation of the active substance 1 part by weight of active ingredient is mixed with the specified amount of solvent which contains the specified amount of emulsifier, and dilute the concentrate with water to the desired concentration.
1 cm der Wirkstoffzubereitung wird auf eine Filterpapierscheibe mit 7 cm Durchmesser aufpipettiert. Man legt sie naß auf ein Glas, in dem sich 50 Taufliegen (Drosophila melanogaster) befinden und bedeckt sie mit einer Glasplatte.1 cm of the active compound preparation is placed on a filter paper disk pipetted on with a diameter of 7 cm. You put them on wet Glass that contains 50 fruit flies (Drosophila melanogaster) and covers them with a glass plate.
Nach den angegebenen Zeiten bestimmt man die Abtötung in #. Dabei bedeutet 100 ^, daß alle Fliegen abgetötet wurden, 0 $> bedeutet, daß keine Fliegei getötet wurden.After the specified times, the destruction is determined in #. 100 ^ means that all flies have been killed, 0 $> means that no fly eggs have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszelten und Abtötungsgrad gehen aus der nachfolgenden Tabelle 1 hervor:Active ingredients, active ingredient concentrations, evaluation tents and The degree of destruction is shown in Table 1 below:
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lamelle 1 (Srosophila-Test) lamelle 1 (Srosophila test)
Wirkstoff Wirkstoffkonzentration inActive ingredient active ingredient concentration in
Abtötungsgrad in fo nach 1 TagDegree of destruction in fo after 1 day
(O2H(O 2 H
0,10.1
(bekannt)(known)
0 (OH3O)2P-0 (OH 3 O) 2 P-
ClCl
0,1
0,010.1
0.01
100 100100 100
(OH-O)0J-(OH-O) 0 J-
ClCl
OH,OH,
Le A 14 0,1
0,01 Le A 14 0.1
0.01
- 13 -- 13 -
100 100100 100
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Tabelle 1 (Fortsetzung) (Drosophila-Test) Table 1 (continued) (Drosophila test)
Wirkatoff Wirkstoffkonzentration inActive ingredient active ingredient concentration in
Abtötungsgrad in i» nach 1 TagDegree of destruction in i » after 1 day
BrBr
0,1
0,010.1
0.01
100 100100 100
IlIl
0,1
0,010.1
0.01
100 100100 100
titi
JSr-. %τ jU^-,,ηJSr - . % τ jU ^ - ,, η
CH, 0,1
0,01CH, 0.1
0.01
100 90100 90
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Tabelle 1 (Fortsetzung) 2241395 (Drosophila- Test) Table 1 (continued) 2241395 (Drosophila test)
WirkstoffActive ingredient
Wirkstoffkonzentration inActive ingredient concentration in
Abtötungßgrad in io nach 1 TagDegree of destruction in io after 1 day
C1 0,1
0,01 C1 0.1
0.01
100 100100 100
0,1
0,010.1
0.01
100 100100 100
0,1
0,010.1
0.01
100 -98100 -98
ClCl
H, 0,1H, 0.1
o,oio, oi
100 100100 100
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Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, das die angegebene Menge Emulgator enthält, und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent which contains the stated amount of emulsifier, and dilute the concentrate with water to the desired concentration.
Mit der Wirketoffzubereitung besprüht man Kohlblätter (Braesica oleracea) taufeucht und besetzt sie mit Raupen der Kohlschabe (Plutella maculipennis).Cabbage leaves (Braesica oleracea) are sprayed with the active ingredient preparation and they are populated with caterpillars of the cabbage moth (Plutella maculipennis).
Nach den angegebenen Zeiten wird der Abtötungsgrad in H bestimmt. Dabei bedeutet 100 £, daß alle Raupen abgetötet wurden; 0 i> bedeutet, daß keine Raupen abgetötet wurden.After the specified times, the degree of destruction in H is determined. £ 100 means that all the caterpillars have been killed; 0 i> means that none of the caterpillars have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle 2 hervor:Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 2 below:
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Tabelle (Plutella-Test) Table (Plutella test)
Wirkstoff Wirkstoffkonzentrat ion inActive ingredient active ingredient concentration in
Abtötungsgrad in ia nach 3 TagenDegree of destruction in general after 3 days
IlIl
(bekannt) 0,1
0,01(known) 0.1
0.01
100 100100 100
C2H5 2C 2 H 5 2
(bekannt)(known)
0 (CH3O)2P-0 (CH 3 O) 2 P-
(CH3O)2P-O-^ sG1 (CH 3 O) 2 PO- ^ s G1
'CH,'CH,
Le A ULe A U
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/r/ r
Tabelle 2 (Portsetzung) 2241395 (Plutella-Test) Table 2 (port setting) 2241395 (Plutella test)
WirkstoffActive ingredient
zentration in fo Active ingredient
centering in fo
in $ nach
3 TagenDegree of destruction
in $ after
3 days
O
(CH3O)2P-On ^P1 O
(CH 3 O) 2 PO n ^ P 1
VUVU
(C2H5O)2 (C 2 H 5 O) 2
ΓΊΓΊ
titi
H3 H 3
CHCH
(C2H5O)2P-O. Cl(C 2 H 5 O) 2 PO. Cl
^K, 0,1 ^ K, 0.1
0,01
0,0010.01
0.001
100100
100100
9595
1414th
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Beispiel C; Jft 2241355 Example C ; Jft 2241355
Myzus-Test (Kontakt-Wirkung)Myzus test (contact effect)
Lösungsmittel: 3 Gewichtsteile Aceton Emulgator: 1 Gewichtsteil AlkylarylpolyglykolatherSolvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, das die angegebene Menge Emulgator enthält, und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent that contains the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.
Mit der Wirkstoffzubereitung werden Kohlpflanzen (Brassica oleracea), welche stark von der Pfirsichblattlaus (Myzus persicae) befallen sind, tropfnass besprüht.Cabbage plants (Brassica oleracea), which are strongly dependent on the peach aphid (Myzus persicae) are infected, sprayed dripping wet.
Nach den angegebenen Zeiten wird der Abtötungsgrad in % bestimmt. Dabei bedeutet 100 %$ daß alle Blattläuse abgetötet wurden, 0 % bedeutet, daß keine Blattläuse abgetötet wurden.After the specified times, the degree of destruction is determined in % . Here, 100% means that all $ aphids have been killed; 0% means that no aphids were killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeitjen und Resultate gehen aus der nachfolgenden Tabelle 3 hervor:Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below:
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3030th
Tabelle (Myzus-Test) Table (Myzus test)
zentrat ion in io Active ingredient con
centrat ion in io
in io nach
1 TagDegree of destruction
in io after
1 day
( Br
(
0,010.1
0.01
90100
90
(bekannt)(known)
(CH3O)2P-O.(CH 3 O) 2 PO.
0,10.1
0,010.01
0,0010.001
100 100100 100
(CH3O)2P-O.(CH 3 O) 2 PO.
ClCl
0,10.1
0,010.01
0,0010.001
100 100100 100
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A*A *
Tabelle (Myzus-Test) Table (Myzus test)
(Portsetzung)(Port setting)
Wirkstoff Wirkstoffkonzentration inActive ingredient active ingredient concentration in
Abtötungsgrad in fo nach 1 TagDegree of destruction in fo after 1 day
(CHO) P-(L(CHO) P- (L.
(CH3O)2P-(CH 3 O) 2 P-
BrBr
'CH,'CH,
(O2H5O)2P-(O 2 H 5 O) 2 P-
■OH,■ OH,
Le A U 595Le A U 595
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Tabelle 3 (Portsetzung) 22 A 1 39 (Myzus-Test) Table 3 (port setting) 22 A 1 39 (Myzus test)
Wirkstoff Wirkstoffkon- AbtötungsgradActive ingredient active ingredient k on degree of destruction
ζ ent rat ion in °ß> in # nachζ ent rat ion in ° ß> in # after
1 Tag1 day
0,1 1000.1 100
[j j| 0,01 100[j j | 0.01 100
0,001 950.001 95
0,1 1000.1 100
0,01 1000.01 100
0,001 700.001 70
0,010.1
0.01
99100
99
Il
5 Ti f 0
Il
5 Ti f
0,010.1
0.01
100100
100
Le A 14 595 - 22 - Le A 14 595 - 22 -
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Tetranychus-Test (resistent)Tetranychus test (resistant)
Lösungsmittel:. 3Gewichtsteile Aceton Emulgator: 1 Gewichtsteil AlkylarylpolyglykolatherSolvent:. 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ethers
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, das die angegebene Menge Emulgator enthält, und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount Solvent containing the specified amount of emulsifier and dilute the concentrate with water to the desired level Concentration.
Mit der Wirkstoffzubereitung werden Bohnenpflanzen (Phaseolus vulgaris), die ungefähr eine Höhe von 10 bi3 30 cm haben, tropfnaß besprüht. Diese Bohnenpflanzen sind stark mit allen Entwicklungsstadien der gemeinen Spinnmilbe oder Bonnenspinnmilbe (Tetranychus urticae) befallen.Bean plants (Phaseolus vulgaris) which are approximately 10 to 30 cm in height are sprayed to runoff with the preparation of the active compound. These bean plants are heavily infested with the common spider mite or spider mite (Tetranychus urticae) at all stages of development.
Nach den angegebenen Zeiten wird die Wirksamkeit der Wirkstoff zubereitung bestimmt, indem man die toten Tiere auszählt. Der so erhaltene Abtötungsgrad wird in 56 angegeben. 100 io bedeutet, daß alle Spinnmilben abgetötet wurden, 0 # bedeutet, daß keine Spinnmilben abgetötet wurden.After the specified times, the effectiveness of the active ingredient preparation is determined by counting the dead animals. The degree of destruction thus obtained is given in FIG. 100 io means that all spider mites have been killed, 0 # means that none of the spider mites have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle 4 hervor:Active ingredients, active ingredient concentrations, evaluation times and The results are shown in Table 4 below:
Le A 14.595 - 23 - Le A 14,595 - 23 -
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Tabelle 4 £241395Table 4 £ 241395
(Tetranychus-Test / resistent)(Tetranychus test / resistant)
Wirkstoff Wirkstoffkonzentration inActive ingredient active ingredient concentration in
Abtötungsgrad in i° nach 2 TagenDegree of destruction in i ° after 2 days
IlIl
CH,CH,
CH. 0,1CH. 0.1
(bekannt) (C2H5O)2P-O.(known) (C 2 H 5 O) 2 PO.
BrBr
0,10.1
(bekannt) (C0H^O)9P- (known) (C 0 H ^ O) 9 P-
(bekannt) 0,1(known) 0.1
Le A ULe A U
- 24 -- 24 -
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SrSr
lamelle 4 (Fortsetzung) 224139S (Tetranyehus-Test / resistent) lamelle 4 (continued) 224139S (Tetranyehus test / resistant)
Wirkstoff Wirkstoffkon- Abtötungsgrad ζ en trat ion in cß> in fo.naoh Active ingredient active ingredient killing degree ζ en occurred ion in c ß> in fo.naoh
2 Tagen2 days
GTT «GTT «
2 5"—P-2 5 "—P-
(bekannt) 0,1(known) 0.1
0 (CH3O)2P-0 (CH 3 O) 2 P-
(CH3O)2P-O.(CH 3 O) 2 PO.
ClCl
CH-0,1 CH-0.1
0,010.01
0,10.1
100 40100 40
100100
O2H5O)2P-(O 2 H 5 O) 2 P- (
CH, 0,1CH, 0.1
0,010.01
100100
4040
IlIl
"P-"P-
Le A 14 0,1 Le A 14 0.1
- 25 -- 25 -
9999
409-609/1.236409-609 / 1.236
etet
Herstellungsbeispiele 22 A 1 Production Examples 22 A 1
CHr-OCHr-O
ti
P-ti
P-
O2H5- -O 2 H 5 - -
Zu einer Mischung aus 15 g (0,1 Mol) 2-Hydroxy-5-methylpyrazolo( 1 t5-(A )-pyrimidin und 15 g Kaliumcarbonat in 100 ml Acetonitril fügt man 16 g (0,1 Mol) O-Äthyläthan-phosphonsäureesterchlorid, wobei die Temperatur des Reaktionsgemisches auf 25 bis 400C ansteigt. Letzteres wird über Nacht gerührt, anschließend filtriert, das Lösungsmittel abdestilliert und der kristalline Rückstand aus einem Ligroin/Essigester-Gemisch umkristallisiert. Man erhält 19 g (71 °ß> der Theorie) O-Äthyläthan-0-/3-methylpyrazolo(1,5-«0 pyrimidin-(2)-yl_7-phosphonsäureester mit dem Schmelzpunkt 760C.16 g (0.1 mol) of O-ethylethane are added to a mixture of 15 g (0.1 mol) of 2-hydroxy-5-methylpyrazolo (1 t of 5- (A) -pyrimidine and 15 g of potassium carbonate in 100 ml of acetonitrile -phosphonsäureesterchlorid, wherein the temperature of the reaction mixture to 25 to 40 0 C to rise. the latter was stirred overnight, then filtered, the solvent distilled off and the crystalline residue from a ligroin / Essigester mixture crystallized. this gives 19 g (71 ° ß> of theory) of O-Äthyläthan-0- / 3-methylpyrazolo (1,5- "0 pyrimidin (2) -yl_7 acid ester of melting point 76 0 C.
1H3 1H 3
Zu 18,5 g (0,1 Mol) 2-Hydroxy-3-chlor-5~methylpyrazol0-(1,5-ai)-pyrimIdim und 15 g Kaliumcarbonat in 100 ml Acetonitril fügt man 16 g (0,1 Mol) 0,0-Dimethyl-thionophosphorsäureesterchlorid mid rührt die Mischung 2 Stunden bei 400C, anschließend bei Raumtemperatur über Nacht nach. Das Reaktions- 16 g (0.1 mol) are added to 18.5 g (0.1 mol) of 2-hydroxy-3-chloro-5-methylpyrazol0- (1,5-ai) -pyrimidim and 15 g of potassium carbonate in 100 ml of acetonitrile. 0,0-dimethyl-thionophosphorsäureesterchlorid mid then the mixture is stirred for 2 hours at 40 0 C, at room temperature overnight after. The reaction
Le A 14 595 - 26 - Le A 14 595 - 26 -
409809/1236409809/1236
wird dann in Wasser gegossen, mit Methylenchlorid ausgeschüttelt, die organische Phase über Natriumsulfat getrocknet, das Lösungsmittel abdestilliert und der Rückstand aus Ligroin/ Essigester umkristallisiert. Man erhält 10,5 g (33 $ der Theorie) OjO-Dimethyl-O-^-chlor-S-methylpyrazolo-O ,5-* )-pyrimidin(2)yl__7-thionophosphorsäureester mit dem Schmelzpunkt 1140C.is then poured into water, extracted with methylene chloride, the organic phase is dried over sodium sulfate, the solvent is distilled off and the residue is recrystallized from ligroin / ethyl acetate. This gives 10.5 g (33 $ of theory) OjO-dimethyl-O - ^ - chloro-S-O-methylpyrazolo, 5- *) -pyrimidin (2) yl__7-thionophosphates with the melting point 114 0 C.
In analoger Weise können die folgenden Verbindungen hergestellt werden:The following compounds can be prepared in an analogous manner will:
Konstitution Physik.Eigenschaften (Schmelzpunkt) Constitution physics properties (melting point)
640C64 0 C
S
11S.
11
900C90 0 C
CH5 CH 5
0
(CH3O)2P-O.0
(CH 3 O) 2 PO.
2 ^ , 0 2 ^, 0
110 C110 C
Le A 14 595 - 27 - Le A 14 595 - 27 -
409809/1236409809/1236
Konstitutionconstitution
Physik.Eigenschaften (Schmelzpunkt) Physics properties (melting point)
CH.CH.
920C92 0 C
S
'P-S.
'P-
940C94 0 C
O)2P-O) 2 P-
•N• N
1CH, 1 CH,
(CH3O)2LlX^(CH 3 O) 2 LlX ^
S
(C2H5O)2P-S.
(C 2 H 5 O) 2 P-
ClCl
96-98°C 80-81 C 880C96-98 ° C 80-81 C 88 0 C
Le A U 595Le A U 595
- 28 -- 28 -
409809/1236409809/1236
Konstitution Physik.EigenschaftenConstitution, Physics, Properties
(Schmelzpunkt)(Melting point)
P J>T P J> T 48°C48 ° C
(OH-O)2P-CL / (OH-O) 2 P-CL /
5 ά ^ ^] 86-87 C 5 ά ^ ^] 86-87 C
■Ν■ Ν
C2H5O SC 2 H 5 OS
a/'VI 8i-83°( a / 'VI 8i - 83 ° (
Le A U 595 - 29 - Le AU 595 - 29 -
40 9809/123 640 9809/123 6
Die als Ausgangsprodukte benötigten 2-Hydroxypyrazolopyrimidinderivate (III) können beispielsweise wie im folgenden beschrieben hergestellt werden:The 2-hydroxypyrazolopyrimidine derivatives required as starting materials (III) can be produced, for example, as described below:
a) HOa) HO
1 Mol Methanol-freies Natriummethylat wird in 400 ml trockenem Äther angeschlemmt und mit 74 g Äthylformiat sowie 58 g Aceton versetzt, wobei die Innentemperatur der Mischung auf 25 bis 270C ansteigt. Man rührt den Ansatz über Nacht und dampft ihn dann im Wasserbad ein, wobei die Badtemperatur 700C nicht übersteigen soll, kühlt das Reaktionsgemisch ab und löst den Rückstand in 400 ml Wasser. Diese Lösung wird zu einer Mischung aus 99 g Aminopyrazolon, 300 ml Wasser und 65 g Eisessig gegeben. Man rührt den Ansatz 3 Stunden nach, saugt den Niederschlag ab, wäscht ihn mit Acetonitril und trocknet das Produkt auf Ton. Es werden 45 g (30 ?£ der Theorie) des 2-Hydroxy-5-methylpyrazolo(i,5-<* )pyrimidine vom Schmelzpunkt 2040C erhalten.1 mole of methanol-free sodium methylate angeschlemmt in 400 ml dry ether and added with 74 g of ethyl formate and 58 g of acetone, keeping the internal temperature of the mixture to 25 to 27 0 C increases. The mixture is stirred overnight and then evaporated him in the water bath, wherein the bath temperature should not exceed 70 0 C, the reaction mixture is cooled and the residue is dissolved in 400 ml of water. This solution is added to a mixture of 99 g of aminopyrazolone, 300 ml of water and 65 g of glacial acetic acid. The batch is stirred for 3 hours, the precipitate is filtered off with suction, washed with acetonitrile and the product is dried on clay. 45 g (30% of theory) of the 2-hydroxy-5-methylpyrazolo (1.5 - <*) pyrimidines with a melting point of 204 ° C. are obtained.
b)b)
HOHO
ClCl
Man löst 45 g (0,3 Mol) des wie unter a) gewonnenen 2-Hydroxy-Le A 14 595 - 30 -45 g (0.3 mol) of the 2-hydroxy- Le A 14 595 - 30 - obtained as under a) are dissolved
409809/1236409809/1236
22^139522 ^ 1395
5-methyl-pyrazolopyrimidins in 4OO ml Eisessig und leitet in diese Lösung bei 7O0C 21,3 g Chlor ein. Nach einstündigem Rühren wird die Reaktionslösung abgekühlt, mit 24 g Natriumhydroxid in 50 ml Wasser versetzt, anschließend die Mischung 2 Stunden auf 400C erhitzt, erneut abgekühlt, der Niederschlag abgesaugt, mit Wasser und Äther gewaschen und auf Ton getrocknet. Es werden 18 g (33 f° der Theorie) 2-Hydroxy-3-chlor-5-methylpyrazolo-(i, 5-o(. )-pyrimidin mit dem Schmelzpunkt 2710C erhalten.5-methyl-pyrazolopyrimidine in 4OO ml of glacial acetic acid and initiates 21.3 g of chlorine in this solution at 7O 0 C. After stirring for one hour, the reaction solution is cooled, mixed with 24 g of sodium hydroxide in 50 ml of water, then the mixture is heated to 40 ° C. for 2 hours, cooled again, the precipitate is filtered off with suction, washed with water and ether and dried on clay. There are obtained 18 g (33 ° f of theory) of 2-hydroxy-3-chloro-5-methylpyrazolo- (i, 5-o (.) Pyrimidine with a melting point of 271 0 C.
c)c)
Zu 45 g (0,3 Mol) des wie unter a) gewonnenen 2-Hydroxy-5-methylpyrazolopyrimidins in 400 ml Eisessig werden bei 700C 48 g Brom, gelöst in 400 ml Eisessig, getropft. Nach einstündigem Rühren kühlt man die Reaktionslösung ab und versetzt sie mit 24 g Natriumhydroxid in 50 ml Wasser. Anschließend wird die Mischung kurze Zeit auf 90 C erhitzt, eine weitere Stunde gerührt, auf ca. 200C abgekühlt, der Niederschlag abgesaugt, mit Äthanol und Äther gewaschen und getrocknet. Es werden 50 g (73 i° der Theorie) 2-Hydroxy-3-brom-5-methyl-pyrazol-(i,5-a)pyrimidin mit dem Zersetzungspunkt 185°C erhalten.48 g of bromine, dissolved in 400 ml of glacial acetic acid, are added dropwise at 70 ° C. to 45 g (0.3 mol) of the 2-hydroxy-5-methylpyrazolopyrimidine obtained as under a) in 400 ml of glacial acetic acid. After stirring for one hour, the reaction solution is cooled and 24 g of sodium hydroxide in 50 ml of water are added. The mixture is then heated to 90 ° C. for a short time, stirred for a further hour, cooled to approx. 20 ° C., the precipitate is filtered off with suction, washed with ethanol and ether and dried. 50 g (73 ° of theory) of 2-hydroxy-3-bromo-5-methyl-pyrazole- (i, 5-a) pyrimidine with a decomposition point of 185 ° C. are obtained.
Le A 14 595 - 31 - Le A 14 595 - 31 -
409803/1236409803/1236
Claims (6)
1 J^P-HaI (II)a X
1 J ^ P-HaI (II)
Priority Applications (22)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2241395A DE2241395C3 (en) | 1972-08-23 | 1972-08-23 | O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters, process for their preparation and their use as insecticides and acaricides |
US05/386,684 US3950337A (en) | 1972-08-23 | 1973-08-08 | O-pyrazolopyrimidine-(thiono)-phosphoric(phosphonic) acid esters |
EG307A EG11169A (en) | 1972-08-23 | 1973-08-09 | O-pyrazolopyrimide-(thiono)-phosphoric(phosphonic)acid esters,process for their production and their use as insecticides and acaricides |
IL43023A IL43023A (en) | 1972-08-23 | 1973-08-20 | O-pyrazolopyrimidine-phosphoric,thionophosphoric,phosphonic and thionophosphonic acid esters,their production and their use as insecticides and acaricides |
JP48093021A JPS4955851A (en) | 1972-08-23 | 1973-08-21 | |
JP48093020A JPS4956994A (en) | 1972-08-23 | 1973-08-21 | |
CH1202173A CH583741A5 (en) | 1972-08-23 | 1973-08-21 | |
TR17237A TR17237A (en) | 1972-08-23 | 1973-08-21 | O-PIRAZOLPIRIMIDIN- (TIONO) -PHOSPHORIC (PHOSPHONIC) ACID ESTERS, PROCESSES SPECIFIC TO ITS MANUFACTURING AND THEIR USE AS INSECTICIDES AND MISCIDES |
IT28053/73A IT1046108B (en) | 1972-08-23 | 1973-08-21 | ESTERS OR PYRAZOLPYRIMIDIN THION PHOSPHORIC PHOSPHONIC PROCESS FOR THEIR PRODUCTION AND THEIR USE AS INSECTICIDES AND ACARICIDES |
LU68278A LU68278A1 (en) | 1972-08-23 | 1973-08-21 | |
ZA735773A ZA735773B (en) | 1972-08-23 | 1973-08-22 | O-pyrazolopyrimide-(thiono)-phosphoric(phosphonic)acid esters,process for their production and their use as insecticides and acaricides |
ES418102A ES418102A1 (en) | 1972-08-23 | 1973-08-22 | O-pyrazolopyrimidine-(thiono)-phosphoric(phosphonic) acid esters |
BR6467/73A BR7306467D0 (en) | 1972-08-23 | 1973-08-22 | PROCESS FOR THE MANUFACTURE OF ESTERS OF 0-PIRAZOLE PYRIMIDIN- (THIONO) - PHOSPHORIC (PHOSPHONIC), AND INSECTICIDES AND ACARICIDES BASED ON THESE |
BE134807A BE803877A (en) | 1972-08-23 | 1973-08-22 | NEW ESTERS OF O-PYRAZOLOPYRIMIDINE- (THIONO-PHOSPHORIC) ACIDS (PHOSPHONICS), THEIR PREPARATION PROCESS AND THEIR APPLICATION AS INSECTICIDES AND ACARICIDES |
DK462673A DK133340C (en) | 1972-08-23 | 1973-08-22 | INSECTICIDES AND ACARICIDES EFFICIENTS O-PYRAZOLOPYRIMIDINE- (THIONO) -PHOSPHOR (PHOSPHON) ACID ESTERS |
AU59521/73A AU475472B2 (en) | 1972-08-23 | 1973-08-22 | O-pyrazolopyrimidine-(thiono)-phosphoric (phosphonic) acid esters, process for their production and their use as insectices and acaricides |
NL7311585A NL7311585A (en) | 1972-08-23 | 1973-08-22 | |
CA179,376A CA1014955A (en) | 1972-08-23 | 1973-08-22 | O-pyrazolopyrimidine-(thiono)-phosphoric (phosphonic) acid esters, process for their production and their use as insecticides and acaricides |
IE1470/73A IE38124B1 (en) | 1972-08-23 | 1973-08-22 | O-pyrazolopyrimidine-(thiono)-phosphoric(phosphonic)acid esters process for their production and their use as insecticides and acaricides |
HU73LE709A HU167412B (en) | 1972-08-23 | 1973-08-22 | Insecticides and acarycides containing o-pirasolpiramidin-/tion/-phosphoric acid-/phosphonic acid/- esthers and process for production of the active substances |
FR7330650A FR2197012B1 (en) | 1972-08-23 | 1973-08-23 | |
GB3993873A GB1397997A (en) | 1972-08-23 | 1973-08-23 | O-pyrazolo-pyrimidine-thiono-phsophoric -phosphinic- acid esters process for their production and their use as insecticides and acaricides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2241395A DE2241395C3 (en) | 1972-08-23 | 1972-08-23 | O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters, process for their preparation and their use as insecticides and acaricides |
Publications (3)
Publication Number | Publication Date |
---|---|
DE2241395A1 true DE2241395A1 (en) | 1974-02-28 |
DE2241395B2 DE2241395B2 (en) | 1979-09-20 |
DE2241395C3 DE2241395C3 (en) | 1980-06-19 |
Family
ID=5854292
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2241395A Expired DE2241395C3 (en) | 1972-08-23 | 1972-08-23 | O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters, process for their preparation and their use as insecticides and acaricides |
Country Status (21)
Country | Link |
---|---|
US (1) | US3950337A (en) |
JP (2) | JPS4956994A (en) |
AU (1) | AU475472B2 (en) |
BE (1) | BE803877A (en) |
BR (1) | BR7306467D0 (en) |
CA (1) | CA1014955A (en) |
CH (1) | CH583741A5 (en) |
DE (1) | DE2241395C3 (en) |
DK (1) | DK133340C (en) |
EG (1) | EG11169A (en) |
ES (1) | ES418102A1 (en) |
FR (1) | FR2197012B1 (en) |
GB (1) | GB1397997A (en) |
HU (1) | HU167412B (en) |
IE (1) | IE38124B1 (en) |
IL (1) | IL43023A (en) |
IT (1) | IT1046108B (en) |
LU (1) | LU68278A1 (en) |
NL (1) | NL7311585A (en) |
TR (1) | TR17237A (en) |
ZA (1) | ZA735773B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2544938A1 (en) * | 1975-10-07 | 1977-04-21 | Bayer Ag | 0-PYRAZOLOPYRIMIDINE (THIONO) - PHOSPHORUS (PHOSPHONE) -AEUREESTER OR. -ESTERAMIDE, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDE, ACARICIDE AND NEMATICIDE |
DE2545881A1 (en) * | 1975-10-14 | 1977-04-21 | Bayer Ag | 0-PYRAZOLOPYRIMIDINTHIONOTHIOLPHOSPHORIC ACID ESTER, METHOD OF MANUFACTURING AND USE AS INSECTICIDES, ACARICIDES AND NEMATICIDES |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2644642C2 (en) * | 1976-10-02 | 1984-09-27 | Bayer Ag, 5090 Leverkusen | Pyrazolopyrimidinyl (thiono) (thiol) phosphorus (phosphonic) acid esters, process for their preparation and their use as insecticides and acaricides |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1239695B (en) * | 1964-12-24 | 1967-05-03 | Bayer Ag | Process for the preparation of phosphorus, phosphonic, thionophosphorus or thionophosphonic acid esters |
IL25184A (en) * | 1965-02-20 | 1970-01-29 | Hoechst Ag | Phosphoric acid esters,process for the manufacture thereof,and their use as pesticides |
CH472435A (en) * | 1965-06-02 | 1969-05-15 | Bayer Ag | Process for the preparation of esters of phosphoric acids |
DE2033947C3 (en) * | 1970-07-08 | 1974-04-11 | Bayer Ag, 5090 Leverkusen | O-pyrazolopvrimidine (thiono) phosphorus (phosphonic) acid esters, processes for their preparation, and insecticides and acaricidal agents |
-
1972
- 1972-08-23 DE DE2241395A patent/DE2241395C3/en not_active Expired
-
1973
- 1973-08-08 US US05/386,684 patent/US3950337A/en not_active Expired - Lifetime
- 1973-08-09 EG EG307A patent/EG11169A/en active
- 1973-08-20 IL IL43023A patent/IL43023A/en unknown
- 1973-08-21 JP JP48093020A patent/JPS4956994A/ja active Pending
- 1973-08-21 LU LU68278A patent/LU68278A1/xx unknown
- 1973-08-21 CH CH1202173A patent/CH583741A5/xx not_active IP Right Cessation
- 1973-08-21 IT IT28053/73A patent/IT1046108B/en active
- 1973-08-21 TR TR17237A patent/TR17237A/en unknown
- 1973-08-21 JP JP48093021A patent/JPS4955851A/ja active Pending
- 1973-08-22 BR BR6467/73A patent/BR7306467D0/en unknown
- 1973-08-22 NL NL7311585A patent/NL7311585A/xx not_active Application Discontinuation
- 1973-08-22 BE BE134807A patent/BE803877A/en unknown
- 1973-08-22 AU AU59521/73A patent/AU475472B2/en not_active Expired
- 1973-08-22 ES ES418102A patent/ES418102A1/en not_active Expired
- 1973-08-22 ZA ZA735773A patent/ZA735773B/en unknown
- 1973-08-22 DK DK462673A patent/DK133340C/en not_active IP Right Cessation
- 1973-08-22 CA CA179,376A patent/CA1014955A/en not_active Expired
- 1973-08-22 IE IE1470/73A patent/IE38124B1/en unknown
- 1973-08-22 HU HU73LE709A patent/HU167412B/en unknown
- 1973-08-23 GB GB3993873A patent/GB1397997A/en not_active Expired
- 1973-08-23 FR FR7330650A patent/FR2197012B1/fr not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2544938A1 (en) * | 1975-10-07 | 1977-04-21 | Bayer Ag | 0-PYRAZOLOPYRIMIDINE (THIONO) - PHOSPHORUS (PHOSPHONE) -AEUREESTER OR. -ESTERAMIDE, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDE, ACARICIDE AND NEMATICIDE |
DE2545881A1 (en) * | 1975-10-14 | 1977-04-21 | Bayer Ag | 0-PYRAZOLOPYRIMIDINTHIONOTHIOLPHOSPHORIC ACID ESTER, METHOD OF MANUFACTURING AND USE AS INSECTICIDES, ACARICIDES AND NEMATICIDES |
Also Published As
Publication number | Publication date |
---|---|
CH583741A5 (en) | 1977-01-14 |
TR17237A (en) | 1976-08-03 |
GB1397997A (en) | 1975-06-18 |
HU167412B (en) | 1976-04-28 |
IL43023A0 (en) | 1973-11-28 |
BR7306467D0 (en) | 1974-06-27 |
AU5952173A (en) | 1975-02-27 |
EG11169A (en) | 1977-11-30 |
IT1046108B (en) | 1980-06-30 |
CA1014955A (en) | 1977-08-02 |
US3950337A (en) | 1976-04-13 |
BE803877A (en) | 1974-02-22 |
IE38124L (en) | 1974-02-23 |
FR2197012B1 (en) | 1977-02-25 |
DK133340C (en) | 1976-09-27 |
DE2241395C3 (en) | 1980-06-19 |
IE38124B1 (en) | 1978-01-04 |
NL7311585A (en) | 1974-02-26 |
LU68278A1 (en) | 1973-10-24 |
DK133340B (en) | 1976-05-03 |
IL43023A (en) | 1976-08-31 |
ZA735773B (en) | 1974-08-28 |
JPS4956994A (en) | 1974-06-03 |
FR2197012A1 (en) | 1974-03-22 |
DE2241395B2 (en) | 1979-09-20 |
AU475472B2 (en) | 1976-08-26 |
ES418102A1 (en) | 1976-03-16 |
JPS4955851A (en) | 1974-05-30 |
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